(-)-1-epi-Castanospermine | 140386-65-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: (-)-1-epi-Castanospermine
• 英文别名: (1S,6R,7S,8S,8aS)-1,2,3,5,6,7,8,8a-octahydroindolizine-1,6,7,8-tetrol
• CAS: 140386-65-8
• 化学式: C₈H₁₅NO₄
• 分子量: 189.211
• InChiKey: JDVVGAQPNNXQDW-BJNUKLAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.2
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  84.2
• 氢给体数：
  4
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (2R,3S,4R,5R,6R)-2,3,4,6-Tetra-O-benzyl-1,5-bis-O-(methoxymethyl)octane-1,2,3,4,5,6,8-heptol 在 palladium on activated charcoal 吡啶 、 咪唑 、 盐酸 、 4-二甲氨基吡啶 、 barium dihydroxide 、 四丁基氟化铵 、 氢气 、 一水合肼 、 三乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 乙醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 60.0 ℃ 、300.0 kPa 条件下， 反应 205.0h， 生成 (-)-1-epi-Castanospermine
  参考文献：
  名称：

  Stereocontrolled total synthesis of the unnatural enantiomers of castanospermine and 1-epi-castanospermine

  摘要：

  A concise practical synthesis (13 steps, ca. 10-12% overall yield) of the unnatural enantiomer of castanospermine ((-)-1) and its 1-epimer 2 from 2,3,4-tri-O-benzyl-D-xylose (3) is described. Key steps in the synthesis are two organometal aldehyde additions, vinylation of 3 to 4 and allylation of 6a to 11, both of which proceed with a considerably high degree of stereocontrol. The fused ring system is generated from the acyclic amino polyol derivative 16a by two successive S(N)2-type cyclizations. Notably, the annulation of the six-membered ring makes use of tetravalent phosphonium reagents (Appel or Mitsunobu type) which cyclize the amino alcohol 22a/b directly to 23a/b without need for N-deprotection and O-activation manipulations.

  DOI：

  10.1021/jo00037a043

文献信息

• Stereocontrolled total synthesis of the unnatural enantiomers of castanospermine and 1-epi-castanospermine
  作者：Johann Mulzer、Henrietta Dehmlow、Juergen Buschmann、Peter Luger

  DOI：10.1021/jo00037a043

  日期：1992.5

  A concise practical synthesis (13 steps, ca. 10-12% overall yield) of the unnatural enantiomer of castanospermine ((-)-1) and its 1-epimer 2 from 2,3,4-tri-O-benzyl-D-xylose (3) is described. Key steps in the synthesis are two organometal aldehyde additions, vinylation of 3 to 4 and allylation of 6a to 11, both of which proceed with a considerably high degree of stereocontrol. The fused ring system is generated from the acyclic amino polyol derivative 16a by two successive S(N)2-type cyclizations. Notably, the annulation of the six-membered ring makes use of tetravalent phosphonium reagents (Appel or Mitsunobu type) which cyclize the amino alcohol 22a/b directly to 23a/b without need for N-deprotection and O-activation manipulations.